CHAPTER – 7 EQUILIBRIUM

• Chemical Equilibrium
In a chemical reaction chemical equilibrium is defined as the state at which there is no further change in concentration of reactants and products.
For example,

Consider a hypothetical reaction,

A + B ↔ C + D

At equilibrium the rate of forward reaction is equal to the rate of backward reaction. Equilibrium 

mixture: The mixture of reactants and products in the equilibrium state is called an equilibrium mixtures.
Based on the extent to which the reactions proceed to reach the state of equilibrium, these may be classified in three groups:
(i) The reactions which proceed almost to completion and the concentrations of the reactants left are negligible.
(ii) The reactions in which most of the reactants remains unchanged, i.e. only small amounts of products are formed.
(iii) The reactions in which the concentrations of both the reactants and products are comparable when the system is in equilibrium.

EQUILIBRIUM IN PHYSICAL PROCESSES

(i) Solid-Liquid Equilibrium: The equilibrium is represented as H2O(S) ↔ H2O(l)
Rate of melting of ice = Rate of freezing of water.
The system here is in dynamic equilibriums and following can be inferred.
(a) Both the opposing processes occur simultaneously
(b) Both the processes occur at the same rate so that the amount of ice and water – remains constant.

(ii) Liquid-Vapour Equilibrium
The equilibrium can be represented as

Rate of evaporation = Rate of condensation
When there is an equilibrium between liquid and vapours, it is called liquid-vapour equilibrium.

(iii) Solid-Vapour Equilibrium
This type of equilibrium is attained where solids sublime to vapour phase. For example, when solid iodine is placed in a closed vessel, violet vapours start appearing in the vessel whose intensity increases with time and ultimately, it becomes constant.

The equilibrium may be represented as I2 (s) ↔ I2 (vapour)

Rate of sublimation of solid I2 to from vapour = rate of condensation of I2 vapour to give solid I2.

• Equilibrium involving Dissolution of Solid in Liquid
Solution: When a limited amount of salt or sugar or any solute dissolves in a given amount of water solution is formed.
At a given temperature state is reached when no more solute can be dissolved then the solution is called saturated solution.
The equilibrium between a solid and its solution is indicated by the saturated solution and may be represented as

Rate of dissolution = rate of precipitation

Sugar (s) ↔ Sugaer (in solution)

Here dissolution and precipitation takes place with the same speed.
On adding a small amount of radioactive sugar to the saturated solution it will be found that the sugar present in the solution as well as in the solid state is radioactive.

• Equilibrium between a Gas and its Solution in Liquid
This type of equilibrium can be seen by the following example:
Let us consider a sealed soda water bottle in which C02 gas is dissolved under high pressure. A state of equilibrium is attained between CO2 present in the solution and vapours of the gas

CO2(g) ↔ CO2 (present in solution)
Henry’s law: The solubility of a gas in a liquid at a certain temperature is governed by Henry’s law. It states that the mass of a gas that dissolves in a given mass of a solvent at any temperature is proportional to the pressure of the gas above the surface of the solvent.

Mathematically,

m p

m = KH p

where, KH = Henry’s constant

• Characteristics of Equilibria Involving Physical Processes
(i) The equilibrium can be attained only in closed systems at a given temperature.
(ii) At the equilibrium the measurable properties of the system remain constant.
(iii) The equilibrium is dynamic since both the forward and backward processes occur at same rate.
(iv) At equilibrium, the concentrations of substances become constant at constant temperature.
(v) The value of equilibrium constant represents the extent to which the process proceeds before equilibrium is achieved.